Derivative of substituted succinic acids



Patented Dec. 5, 1939 UNITED STATES PATENT o1=1=1c15 DERIVATIVE F SUBSTITUTED SUCCINIC ACIDS No Drawing.

rial No. 132,095.

9 Claims.

This invention relates to technically valuable derivatives of substituted succinic acids and a process for the manufacture of the same.

The process of manufacture in accordance with the invention is by converting succinic acids substituted in at least one of their methylene groups by at least one saturated or unsaturated hydrocarbon radicle containing at least five carbon atoms, and particularly those containing at least 10 eight carbon atoms, into derivatives in which at least one acid hydroxyl group is substituted by an amino radicle. These derivatives are characterized by high capillary activity and accordingly are suitable as wetting-, washing-, emulsifying-,

. dispersingand permeating agents.

Among succinic acids of the kind specified,

' adapted for use in the present invention may be mentioned succinic acids, substituted by at least one saturated alkyl radicle of at least 5 carbon atoms, such as isoamyl succinic acid, hexyl succinic acid, cyclohexyl succinic acid, heptyl succinic acid, octyl succinic acid, isododecyl succinic acid and pentadecyl succinic acid, the anhydrides of these acids being obtainable for example in accordance with the co-pending application Ser.

No. 733,126, filed June 29, 1934, now U. S. Patent No. 2,121,183, dated June 21, 1938, by condensing saturated hydrocarbons, such as pentane, hexane, cyclohexane, heptane, octane, isododecane, pentadecane, with maleic anhydride. Furthermore succinic acids substituted by an unsaturated alkyl radicie of at least 5 carbon atoms, such as amylene succinic acid, hexene succinic acid, cyclohexene succinic acid, isododecylene succinic acid and pentadecylene succinic acid are suitable for the purpose of this invention, the anhydrides of these acids being obtainable for example by condensing the corresponding olefines, such as amylene, nonylene, hexene, cyclohexene, 4o isododecylene and pentadecylene with maleic anhydride (compare French Patent No. 801,919). Finally are to be mentioned succinic acids substituted by an aralkyl radicle, such as 'y-methyl- 'y-phenylpyrotartaric acid and y-phenyl-w-di- 45 methylpyrotartaric. acid, anhydrides of succinic acids of this type being obtainable for example by the process of the co-pending application Ser. No. 733,126 by condensing aliphatic hydrocarbons substituted by an aromatic radicle, such.as 50 toluene, ethyl benzene, diethyl benzene, propyl benzene and isopropyl benzene, diisopropyl benzene, triisopropyl benzene, tetrahydronaphthalene, etclfwith maleic acid anhydride.

For the manufacture of the derivatives con- 5 taming an amino radicle the ac ds Bush or Application March 20, 1937, Se-

In Germany March 21, 1936 especially suitable derivatives such as for examplc the anhydrides, chlorides or esters of the succinic acids of the kind specified may be employed.

' For the introduction of the amino radicle the above mentioned compounds are caused to react with compounds containing an amino radicie carrying at least one hydrogen atom bound to the nitrogen atom. As such compounds comprising amino radicles may be employed, for example, ammonia, primary and secondary aliphatic amines, such as, for example, monomethylamine, dibutylamine, diisopropylamine, octylamine, cetylamine, hydroxy-ethylamine, primary and secondary aromatic amines, such as aniline, toluidine, xylidine, chloraniline, nitraniline, ethylaniline, diphenylamine, a-naphthylamine, benzylamine, amines of the alicyclic series, such as cyclohexylamine, amino carboxylic acids, such as glycocoll and anthranilicacid, and also amino sulphonic acids, such as taurine, aminobenzene sulphonic acids,,naphthylamino sulphonic acids, etc.

In many cases it is advisable to carry out the condensation in the presence of aninert solvent, such as for example, benzene, benzine, ligroine, chloroform, carbon tetrachloride, dioxane, etc.

In the conversion of the acids or suitable derivatives thereof in the process of the present invention the corresponding dicarboxylic acid monoamides are generally formed first by substitutlng one acid hydroxyl group.

When employing the anhydrides, chlorides or esters of the succinic acids of the kind specified this substitution begins in general already at ordinary temperature under evolution of heat when mixing the components. When employing the acids themselves in general a gentle heating is sufllcient to initiate the reaction. When the dicarboxylic acid monoamides still contain a hydrogen atom linked to a nitrogen atom, as is the case when ammonia or primary amines respectively derivatives thereof are employed, the di'- carboxylic acid monoamides can be converted by heating to the corresponding imides. This conversion takes place in general at a temperature over about C. and especially in a temperature range of about C. to about 200 C.

When employing a considerable excess of the specified compounds containing an amino radicle, especially an excess of a secondary amine, in the presence of an agent which splits oil water, the dicarboxylic acid diamides are generally obtained. As agents splitting off water can be emplayed, for example, hydrosilicates, such as the the invention, without'being restricted thereto;

the parts are by weight:

sample 1 Propylene gas is passed into 1000 parts by weight of phosphoric acid in a copper autoclave fitted with a stirring device at 150-180 C. and a pressure of 30 atmospheres gauge. The reaction proceeds erothermically with the result that after the period of initial heating no further supply of heat is necessary. The autoclave may be fitted with a cooling device in order to avoid over=heating After 1 hour 1000 parts by weight of polymerization product have collected in the autoclave. The product is an oily liquid of faintly yellowish color. It is purified by distillation.

By fractional distillation of this product one fraction is obtained distilling from about to about C. consisting mainly of unsaturated hydrocarbons of the formula CaHm having a specific gravity of OMS/16, an index of refraction and an octalne number of 78.

After careful drying, 1000 parts by weight of this polymerization product are heated in an autoclave fitted with a stirrer for 1% hours at 215-220 C. with 200 parts by weight of maleic anhydride and 200 parts by weight of benzene. A super-pressure of 15-20 atmospheres is thereby attained. After cooling, the gaseous reaction products are blown off. The yellowish reaction mixture is then freed from unchanged starting material by distillation under reduced pressure and a yellowish brown viscous oil, the greater portion of which, consisting of nonylene succinic anhydride, distils over at 1'70-195 C. under 12 mm. is obtained as residue.

onia is passed at about 40-60 C. with cooling and brisk stirring into 336 parts by weight of the anhydride of isononylene succinic acid. After about one hour isononylene succinic acid monoamide is formed in a quantitative yield. It forms a dough-like mass with an acid value of 250.

Analysis gave the following results:

Found: Calculated for CzzHssOsN: c=s4.s% c=s .v5% n=9.'z5% n=s.c2% N=5.4% u=5.a%

By heating the acid to 150-160 C. water is split ofi and isononylene succinic acid imide is obtained as a yellow, extremely viscous oiL-boiling at 202-205 C. under apressure of 9 mm. The imide dissolves'in dilute caustic soda lye and also in dilute sodium carbonate solution.

Analysis of the oil gave the following results:

Found: Calculated for C13H2102N:

C=70.2% C=69.9%. H=9.3% H=9.49% N=5.6% N=6.28%

Example 2 120 parts by weight of aniline are caused to hydroxyethylamide.

arcane drop into 260 parts by weight of isododecylene succinic acid anhydride, which is stirred briskly. The temperature rises to 92 C. On heating to about C. the resulting isododecylene succinic acid monoanilide is converted to dodecylene suc- 5 cinic acid phenylimlde, which is obtained as a dark yellow, viscous oil boiling at 233-237 C. under s. pressure of 8 mm. and the constitution of which corresponds with the formula CssHsrOzN. Analysis gave the following results:

Found; Calculated for CzzHnOzN:

C='Z7.05% C=77.36% H=8.72% 3:93.69;

Example 3 150 parts by weight of n-butylarnine are caused to drop into 224 parts by weight of isononylene succihic acid anhydride, which is stirred. The temperature rises to about 100 C. By further heating to C. the isononylene succinic acid mono-n-butylannde is converted by the splitting oil of water to isononylene succinic acid n-butylimide, which is obtained as a yellow, viscous oil boiling at 187-192 0. under a pressure or s 25 mm. and the composition of which corresponds with the formula CnHzaOsN.

Analysis of the oil gave the following results:

Found: Calculated for CnHzaOzN:

C='l3.0% C=73.05% H=10.4% -n=1o.47% N=4.65 N=5.02%

Example 4 135 parts by weight of ethanolamine are caused to drop into 336 parts by weight of isononylene succinic acid anhydride, which is stirred.- The temperature rises to 137 0. Water commences to split off at about 150 C. and ceases at about 200 C. The resulting isononylene succinic acidp-hydroxyethylimide is obtained as a thick, yellow, strongly fluorescent oil, boiling at 200-212' C. under a pressure of 7 mm. It is distinguished from the foregoing imide substituted on the nitrogen atom by a hydrocarbon residue by the fact that it dissolves in dilute caustic soda lye with opening of the ring and formation of the sodium salt of isononylene succinlc acid mono- The analysis of the oil gave the folio sults:

Found:

c=67.1% H=9.46% N=5.3%

Calculated for CmHstOaN:

, c=67.2% H=9.45% N=5.2%

Example 5 224 parts by weight of isononylene succinic acid anhydride are caused to drop into 180 parts by weight of melted smenylene diamine,

I which is stirred briskly. The temperature of the C. under a pressure of 9 mm. andwhich dissolves in dilute hydrochloric acid.

Analysis gave the following values:

Found: Calculated for CwHzaOzNs:

C=72.88% C=72.56% H=8.33% H=8.84%

Example 6 A mixture of 400 parts by weight of isododecylene succinic acid anhydride and parts by weight of glycocoll is heated with stirring to about 0.; this temperature is then maintained for approximately one hour. The resulting dicarboiqlic acid monoamide, the composition of which corresponds to the formula CrsHarOsN, is obtained as a yellow, viscous mass. Analysis:

Found: Calculated for C1aH31O5N2 C=63.4% C=63.3% H=8.97% H=9.16% N=4.0% N=4.11%

By further heating the dicarboxylic acid monoamide water begins to split off at about C. and the evolution is completed at about 200 C. The isododecylene succinic acid-imido acetic acid is obtained as a dark yellow resin, boiling at 260-265 C. under a pressure of 12 mm.

Analysis gave the following results:

Found: Calculated for C1sHz9O4N:

C=66.6% C=66.83% H=8.8% H=9.04% N=4.05% N=4.33%

Example 7 A mixture of 220 parts by weight of p-aminophenol and 532.4 parts by weight of isododecylene succinic acid anhydride is heated with stirring. At about 140 C. water commences to split of]? slowly and the evolution is complete at C. The isododecylene succinic acid-p-hydroxyphenylimide cannot be distilled. It is obtained as a dark brown, viscous resin, possessing the formula CazHarOaN.

Analysis of the resin gave the following results:

Found: Calculated for C22H31O3N2 c=73.60% c=73.90% H=8.51% H=8.68% N=4.13% N=3.92%

Example 8 A mixture of 266 parts by weight of isododecylene succinic acid anhydride and parts by weight of the sodium salt of sulphanilic acid is heated with stirring. The reaction begins at about 120 C. and is complete at 200 C. After cooling the reaction product is obtained as a bright brown glass, which can be pulverised to a colourless powder.

A nitrogen estimation gave a content of 3.12% nitrogen, while for a compound of the constitution CazHaoSOsNNa. the calculated nitrogen content amounts to about 3.13%.

Example 9 A mixture of 266 parts by weight of isododecylene succinic acid anhydride and 150 parts by weight of the sodium salt of p-alninoethane sulphonic acid is heated with stirring. Water begins to split off at about 160 C. and the evolution is complete at 200 C. The temperature is then still further raised to 210 C. The resulting dark yellow, viscous oil solidifies on cooling to .a dark yellow glass, which can be ground to a white powder. The quantity of water split off amounts to 17 parts.

A nitrogen estimation gave a content of 3.37% nitrogen, while for a compound of the constitution C1aHaoO5NSNa the calculated nitrogen content amounts to 3.54%.

Example 10 130 parts by weight of freshly distilled N-ethylaniline are caused to run into 224 parts by weight of isononylene succinic acid anhydride, which is stirred. The temperature rises to 40 C. without the application of heat and is brought to about 100 C. by heating. The yellow viscous reaction product is neutralised with dilute caustic soda lye and the solution is then evaporated to dryness. The residue, the sodium salt of isononylene succinic acid mono-N-phenyl-N-ethylamide is a bright brownglass, which can be ground to a white powder.

A nitrogen estimation gave a content of 3.72% nitrogen while for a. compound of the constitution CziHsoOaNNa the calculated nitrogen content amounts to 3.82%.

By acidifying the aqueous solution of the sodium salt isononylene succinic acid mono-N- phenyl-N-ethylamide is obtained as a dark yellow, viscous oil, which on distillation splits to isononylene succinic acid anhydride and N- ethylaniline.

Analysis of the crude product gave the following results:

Found: Calculated for CzrHzrOsN:

C=72.83% C=72.99% H=9.02% H=9.05% N=3.8% N=4.06%

Example 11 A mixture of 112 parts by weight of isononylene succinic acid anhydride, 360 parts by weight of diethylamine and 40 parts by weight of the large surface hydrosilicate' known in the commerce under the trade name Tonsil is boiled under reflux for about 10 hours. After cooling the mixture is filtered and the filtrate distilled first under ordinary pressure and subsequently under reduced pressure. The isononylene succinic acid di-diethylamide is obtained as a dark yellow, viscous oil boiling at 195-205 C. under a pressure of 10 mm.

A nitrogen estimation gave a content of 7.64% nitrogen whilefor a compound of the constitution C21H40O2N2 the calculated nitrogen content amounts to 7.95%.

Example 12 45 parts by weight of n-butylamine are dropped into 149 parts by weight of isotetradecylene succinic acid anhydride by stirring. The temperature rises at 105 C. The reaction product forms a semi-solid mass which is neutralised with a 30% sodium lye. The aqueous solution is dried in vacuo, the sodium salt of the isotetradecylene succinic acid mono-n-butylamide remains as a whltepowder.

This powder showed a content of 3.30% o nitrogen, calculated for CaaHwOaNNa 3.55% nitrogen.

I claim:

.1. A succinic acid substituted in one of its methylene groups by one aliphatic hydrocarbon radicle containing at least 8 carbon atoms and at least one acid hydroxyl group of which is substituted by an amino radicle.

2. A succinic acid substituted in one of its methylene groups by one aliphatic hydrocarbon radicle containing at least 8 carbon atoms said radicle being selected from the group consisting of a saturated aliphatic hydrocarbon radicle, an unsaturated aliphatic hydrocarbon radicle and an aralkyl radicle, at least one acid hydroxyl aiaai'ie group of whichissubstituted by an oradicle. stituted in one of its methylene groups by an 3. A succlnic acid substituted in one of its unsaturated aliphatic hydroca 'bon radicle conmethylene groups by one unsaturated aliphatic taming at least 8 carbon atoms. hydrocarbon radicie containing at least 8 carbon 1. Esododecyienesuccinic acid imido acetic acid 5 atoms and at least one acid hydrcxyi group of forming a resin boiling at 260-265 C. under a 5 which is substituted by an ac raoicle. pressure of 12 mm.

a. A succinic acid imid'e substituted in one of 8.4% succinic acid monoamide substituted in its methylene groups by one unsaturated aliphatic one of its methylene groups by one unsaturated hydrocarbon raclicle containing at least 8 caraliphatic hydrocarbon radicle m: A at least 5. Isononyiene succinic acid de forming a 9. The sodium salt of isotetradecylene succinic viscous oil boiling at ZOE-205 C. under a pressure acid mono-n-butylamide forming a, white powder. of 9 mm.

6. A succinic aciti imide carboxyiic acid sub- 10 hon atoms. 8 carbon atoms. t 

